CS270540B1 - Method of ecologically unobjectionable admixture production into road, building-insulating bituminous materials - Google Patents

Abstract

The solution concerns the way of production ecologically not add to the honest and. building-insulating bitumen materials processing dastilizing residues from to produce N-cyclohexylbenzothiazolyl-2-sulfenamide direct oxidation condensation of the crude 2-mercaptobenzothiazole with hypochlorite sodium in excess of cyclohexylamine, emerging in the technological node of regeneration excess cyclohexylamine used as the bottom phase of an emollient heel product of the atoeferic deetillation cyclohexylamine. The lower phase of this primary emollient heel product ea distillation at a pressure of 0.5 to 20 and a temperature of 20 to 150 DEG C., obtained heterogeneously distillate directly or split to an aqueous phase containing cyclohexylamine and the benzothiazole phase returns into the process of producing N-cyclohexylbenzothiazolyl-2-sulfenamide and emollient the residue is taken as an additive to honest and building-insulating bitumen materials. Distillation process the lower phase of the primary emollient heel The product can be worn in two degrees, while at the first stage at pressure of 5 to 20 kPa and a temperature of 20 to 100 ° C isolating the cyclohexylamine-containing aqueous phase and in a second stage at a pressure of 0.5 to 5 kPa and 100 to 150 ° C benzothiazole vase. The solution can be used in the chemical industry.

Description

The present invention relates to a process for the production of an environmentally friendly additive for honest and structural insulation bituminous materials by treating distillation residues from the production of N-cyclohexylbenzothiazol-2-sulfenamide by direct oxidative condensation of crude 2-mercaptobenzothiazole with sodium hypochlorite in excess cyclohexylamine to form excess cyclohexylamine.

In all industrial processes for the preparation of N-cyclohexylbenzothiazolyl-2-sulfenamide, which is used as a vulcanization accelerator, the basic intermediate is 2-mercaptobenzothiazole, which is obtained by high-pressure synthesis from aniline, carbon disulfide and sulfur at temperatures of 250 to 320 ° C. In discontinuous, resp. In continuous reactors, 2-mercaprobenzothiazole is formed in the force of the crude melt with a circulation of the pure component of 85 to 90% by weight. Prior to further processing to N-cyclohexylbenzotazolyl-2-sulfenamide, this basic intermediate is refined, most often boiled in strong mineral alkalis. The refining steps complicate the process for the production of N-cyclohexylbenzothiazolyl-2-sulfenamide! and I'm getting worse! its economic and ecological parameters. CS 215 179 and CS 225 046 describe an efficient process for the preparation of N-cyclohexylbenzothiazole-2-sulfenamide, based on the direct oxidative condensation of crude 2-mercaptobenzothiazole with sodium hypochlorite in excess cyclohexylamine. In this preparation process, it is not necessary to include expensive refining steps in the process, since the role of refining agent is cyclohexylamine used in a 2.5 to 2.95-fold molar excess, at temperatures of 36 to 48 ° C, in a reaction medium with a high input concentration of 2 -aercaptobenzothiazole in the range of 0.90 to 1.40 moles per liter of solution of cyclohexylammonium dibenzothiazolyl-2-mercaptide formed. In practice, a crude melt of 2-aeraptobenzothiazole prepared in a continuous high-pressure reactor from aniline, carbon disulfide and sulfur according to CS 197 513, freed of volatile constituents at atmospheric pressure at atmospheric pressure, especially benzotlazole, pre-purified with gaseous inert carrier 512 . CS 230 287. The oxidative condensation of the 2-mercaptobenzothiazole thus obtained with sodium hypochlorite in excess cyclohexylamine is carried out according to CS 215 179 or CS 225 046 with the possibility of continuous process according to CS 263 560 in a plant according to CS 261 448 or CS 261 692.

The reaction mixture after oxidative condensation is a three-component solid phase system of N-cyclohexylbenzothiazolyl-2-sulfenamide suspended in an emulsified system called organic and aqueous phases. After separation of N-cyclohexylbenzothiazolyl-2-sulfenamide by filtration, the mother liquors are separated into two clear phases from which a and the excess cyclohexylamine are regenerated by distillation at atmospheric pressure according to CS 221 005. Regeneration of cyclohexylamine from the aqueous phase. which contains only sodium chloride from the hypochlorite used is not demanding and the degree of yield reaches 0.99. The problems are concentrated in the area of regeneration of cyclohexylamine from the organic phase, which contains all contaminants from crude 2-mercaptobenzptlazole, as well as by-products of the oxidation of cyclohexylammonium benzothiazolyl-2-mercaptide to the desired N-cyclohexylbenzothiazolyl-2-sulfenamide. In addition to free cyclohexylamine, unreacted 2-mercaptobenzothiazole is present in the organic phase, which binds cyclohexylamine in the form of cyclohexylammonium benzothiazolyl-2-mercaptide. To liberate the cyclohexylamine from the ionic bond to 2-mercaptobenzothiazole ₍ as well as to the subsequent benzothiazolyl-2-sulfinic acid and benzothiazole-2-sulfonic acid), an aqueous solution of a minial alkali in enamel CS 249 497 or CS 249 497, respectively, is preferably used in the distillation at atmospheric pressure. PV 8669-87 CS274352 /, thus achieving a degree of yield above 0.99. In this case, both phases representing the bottom product of the distillation column also find practical use, which significantly improves not only the economy but also the ecology of the N-cyclohexylbenzothiazolyl-2-sulfenamide production process. The aqueous phase of the sodium salts of 2-mercaptobenzothiazole and benzothiazolyl-2-sulfinic and benzothiazol-1-sulfonic acids is refined with lime milk and the clear solution thus purified is used to produce 2-mercaptobenzothiazole of technical scale or to produce subsequent oxidation and oxidation-condensation products based on it. The lower chain of the primary amorphous heel pro2

The product contains 2 to 21% by weight of benzothiazole, 1 to 10.0% by weight of cyclohexylamine, 0.7 to 3.6% by weight of other cycloaliphatic substances, 60.4 to 96.2% by weight of sulfur polycondensants per base of benzothiazole and 2-substituted benzothiazole and 0.1 to 5% by weight of emulsified water and can be used for the addition of honorary and construction-insulating bitumens with a positive effect on their physico-mechanical parameters. However, such a use of the lower phase of the primary pitch sweat product has several significant disadvantages.

One of the most important is the fact that significant amounts of expensive cyclohexylamine and benzothiazole are thus lost, making the production process of N-cyclohexylbenzothiazolyl-2-sulfenamide more expensive. No less serious shortcomings are the unfavorable hygienic-toxicological and ecological consequences of the application of the pitch product in question to bitumens. In practice, the mixing of the bitumen components with the resinous heel product takes place at processing temperatures above 250 ° C, at which several health-promoting components, including cyclohexylamine and benzothiazole, are released into the air, which significantly impairs the hygienic-toxicological characteristics of the working environment. In addition, the remaining proportions of benzothiezole and cyclohexylamine have negative secondary environmental effects, since they are leached out of the additive bitumens.

These deficiencies are eliminated by the process of producing an environmentally friendly additive for honest and structural insulation bitumen materials by treating distillation residues from the production of N-cyclohexylbenzothiazolyl-2-sulfenamide by direct oxidative condensation of crude 2-mercaptobenzothiazole with sodium hypochlorite in excess cyclohexylamine to form excess cyclohexylamine. the lower phase of the resinous bottom product of atmospheric distillation of cyclohexylamine from the organic phase, consisting of benzothiazole, cyclohexylamine, other cycloaliphatic substances, sulfur polycondensers based on benzothiazole e 2-substituted and emulsified water, according to the invention. SUMMARY vynálefau is that the bottom phase of said further primary tarry bottom product was distilled at a pressure of 0.5 to 20 mbar and a temperature of 20 ⁰ to 150 DEG C., the resulting heterogeneous distillate or an average of the distribution of the aqueous phase containing the cyclohexyl amine and the benzothiazole phase is returned to the process for the production of N-cyclohexylbenzothiazolyl-2-sulfenamide and the tarry distillation residue ea is removed as an additive to honorary and construction-insulating bitumen materials. The process of distillation of the lower phase of the primary tarry bottom product can result in two stages, a first stage is at a pressure of 5-20 bar and a temperature of 20 ⁰ to 100 ° C recovered aqueous phase containing the cyclohexyl amine and the second stage at a pressure of 0.5 to 5 teplotě.100 psi and ⁰ to 150 DEG C. benzothiazole phase being returned to the process for preparing N-cyklohexylbenzotiazolyl-2-sulfenamide and the tarry distillation residue is removed at the abovementioned end.

The choice of one- or two-stage distillation process of components convertible to N-cyclohexylbenzothiazolyl-2-sulfenamide is governed by the involvement of technological nodes of the whole production complex and has wide flexibility in relation to the possibility of direct use of distillate. organic benzothiazole phase.

The process for the production of an environmentally friendly additive for honorary and construction-insulating bituminous materials according to the invention by the use of hitherto untrapped proportions of expensive cyclohexylamine and benzothiazole significantly improves the economic parameters of the N-cyclohexylbenzothiazolyl-2-sulfenamide production process and at the same time distillation residue as a secondary raw material.

Example 1

Weigh 625 g (520 ml) into a 1 l boiling flask of the reduced pressure distillation apparatus.

CS 270 540 B1 of the lower phase of the primary resinous bottom product of a column for atmospheric distillation of cyclohexylamine from an organic phase composed in% by weight of water4,9 benzothiazole20,7 cyclohexylamine9,8 cycloaliphatic substances other.

sulfur polycondensation components based on benzothiazole approx. 60

A total of 233 g of heterogeneous mixture is distilled off while the pressure is gradually reduced from 20 kPa to 0.5 kPa and the batch temperature rises from 20 DEG C. to 150 DEG C. On standing, the distillate is divided into 2 phases. The upper aqueous phase, weighing 32.8 g, contains 4.9% of cyclohexylamine and 0.96% of benzothiazole. The lower phase of the distillate, weighing 200.2 g, contains 61.5% of benzothiazole, 27.6% of cyclohexylamine and 10.8% of other cycloaliphatic substances. Both phases are used in the production cycle of N-cyclohexylbenzothiazolyl-2-sulfenamide, or for other purposes. The treated distillation residue weighing 385 g is freed of water and bulk up to 95% of the flood sensory substances present. This distillation residue is used for the environmentally friendly production of mixed honorary and construction-insulating bitumens.

Example 2

625 g (520 ml) of the lower phase of the primary resinous sweat product of the column are weighed into a 1 l boiling flask of the dehydration apparatus under reduced pressure by non-ethno-distillation of cyclohexylamine from an organic phase having a composition in% by weight: water 2,6 benzothiazole11,3 cyclohexylamine4,8 cycloaliphatic substances other sulfur polycondensation components based on benzothiazole approx79

A total of 125.7 g of a heterogeneous mixture was distilled off under the conditions described in Example 1, from which 17.1 g of an aqueous phase containing 5.3% of cyclohexylamine and 0.77% of benzothiazole were removed. The lower phase, weighing 108.6 g, contains 61.8% of benzothiazole, 26.3% of cyclohexylamine and 1.8% of other cycloaliphatic substances. The use of the individual phases of the distillate and the treated detonation residue weighing 493 g, free from up to 96% of the flooding sensory substances, is the same as in Example 1.

Example 3

625 g (520 ml) of the lower phase of the primary resinous bottom product of a column for the atmospheric distillation of cyclohexylamine from an organic phase with a composition in% by weight are weighed into a 1 l boiling flask of a dehydration apparatus under reduced pressures:

water0,1 benzothiazole5,6 cyclohexylamine1,2 cycloaliphatic substances other0,7 sulfur polycondensation components based on benzothiazole cca92

A total of 46.2 g of a heterogeneous mixture containing 1.5% emulsified water, 15.8% cyclohexylamine, 73.6% benzothiazole and 9.0% other cycloaliphatic substances are distilled off under the conditions described in Example 1. Due to the low water content, the distillate is used directly for the pressure synthesis of 2-mercaptobenzothiazole in the production of N-cyclohexylbenzothiazolyl-24 CS 270 540 Bl

-sulfenamide. The utilization of the treated distillation residue with a weight of 572.5 g free of up to 97% of the flooding sensory substances is the same as in Example 1.

Example 4

Weigh 625 g (520 ml) of the lower phase of the primary resinous bottoms of a column for atmospheric distillation of cyclohexylamine from an organic phase with a composition in% by weight of water: water 0,1 benzothiazole5,6 cyclohexylamine1,2 cycloaliphatic substances other0,7 sulfur polycondensation components based on benzothiazole approx92

Under the conditions described in Example 1, a total of 46.2 g of a heterogeneous mixture containing 1.5% emulsified water, 15.8% cyclohexylamine, 73.6% benzothiazole and 9.0% other cycloaliphatic substances are distilled off. Due to the low water content, the distillate is used directly for the pressure synthesis of 2-mercaptobenzothiazole in the production of N-cyclohexylbenzothiazolyl-2-sulfenamide. The utilization of the treated distillation residue with a weight of 572.5 g, free from up to 97% of the flooded condensates, is the same as in Example 1.

Example 4

The batch, the composition of the resin product and the distillation apparatus are the same as in Example 1. In this case, however, the distillation is carried out in 2 stages. In the first stage, 34.1 g of water containing 4.7% of cyclohexylamine and 0.95% of benzothiazole are distilled off at a gradually reducing pressure from 20 kPa to 5 kPa and a batch temperature rising from 20 DEG C. to 100 DEG C. In the subsequent second step, 203.6 g of benzothiazole fraction containing 60.3% of benzothiazole, 29.1% of cyclohexylamine and 10.5% of other cycloallphatic substances are distilled off from the residual dehydrated water at a pressure of 5 kPa and a temperature of 100 ° C to 150 ° C. . The treated distillation residue, weighing 381 g, is freed of water and 96% of the sensory substances present in the flood. Use of distillation fractions! and the resulting distillation residue is the same as in Example 1.

Example 5 '

The batch, the composition of the resin product and the distillation apparatus are the same as in Example 2. In the first stage, 17.6 g of water containing 5.8% of cyclohexylamine are distilled off at a pressure of 20 kPa to 5 kPa and a batch temperature of 20 ° C to 100 ° C. and 0.89 benzothiazole. In the second step, 110.9 g of a benzothiazole fraction containing 61.5% of benzothiazole, 25.4% of cyclohexylamine and 13.0% of water are distilled off from the residual dehydrated at a pressure of 5 kPa to 0.5 kPa and a temperature of 100 DEG C. to 150 DEG C. % of other cycloallphatic substances. The utilization of the fractions and the resulting distillation residue with a weight of 490.2 g free of up to 97% of the flooding sensory substances is the same as in Example 1.

Example 6

The batch, the composition of the pitch product and the distillation apparatus are the same as in Example 3. In the first stage, 0.7 g of water containing 7.8% of cyclohexylamine are distilled off at a pressure of 20 kPa to 5 kPa and a batch temperature of 20 ° C to 100 ° C, and 0.92% benzothiazole. In the second step, 46.2 g of a benzothiazole fraction containing 73.9% of benzothiazole, 15.7% of cyclohexylamine and 10.3% of other cycloalphatic substances are distilled off from the residual dehydrated at a pressure of 5 kPa and a temperature of 100-150 ° C. Use faction! and the resulting distillation residue and a weight of 571.8 g free of up to 97.5% of the flooded sensory substances is the same as in Example 1.

I

CS 270 540 Bl 5

Example 7

Weigh 625 g of pitch product with a composition in% by weight:

water2,5 benzothiazole18,9 cyclohexylamine 2,7, cycloaliphatic substances other2,1 sulfur polycondensation components based on benzothiazole approx. 74%

In the first step, at a pressure of 20 mbar and at a mixture of 200 ⁰ to 100 ° C. was distilled off

16.6 g of water containing 5.1% of cyclohexylamine and 0.85 χ of benzothiazole. In the second stage, 144.1 g of a benzothiazole fraction containing 80.2% of benzothiazole and 10.9% of cyclohexylamine are distilled off from the residual water at a pressure of 5 kPa to 0.5 kPa and a temperature of 100 DEG C. to 150 DEG C. The content of other cycloaliphatic substances aa is in the range of 8.8%. Modified daster. the remainder weighing 458 g is dewatered with up to 98% of the flood sensory substances present. Use of both factions! and the dry distillation residue is the same as in Example 1. '

The toxicological properties of the solid waste from the production of Sulfenax CB / E were evaluated after leachability in distilled water (10 g in 1 water for 24 hours). Genotoxicity at the chromosomal and genomic levels was not evident. Mutagenicity has not been demonstrated in the Tradascantia 4430 strain model.

Example 8

The application properties of toxicologically harmless solid wastes from the production of Sulfenax CB / E were verified on asphalt concrete type mixtures. The waste resins were used in combination with PB - 25 in a ratio of 1: 1, using 4% of the asphalt content of the mixture. AP - 65 and A - 80 asphalt was used as a base. Samples for the test were prepared at 150 and 195 ° C. The results according to the Marshall methodology are shown in tables no. 1 and 2, using mixtures of:

A - basic joint asphalt AP - 65.

B - basic binder asphalt AP - 65 + 4% PB - 25 / commercial additive / C - basic binder asphalt A- 65 ♦ 4% PB - 25 + 4% solid waste from production Sx - CB / E

D - basic binder asphalt A- 80 + 4% PB- 25 + 4% solid waste from production Sx - CB / E

Table 1

Temp. ° C Monitored property A Mixture AB 8 C 0 CSN requirement 150 Stability kN 9.7 10.8 15.9 16.4 min. 9.0 Deflection 10 ” ¹ mm 49.3 47.2 41.5 32.3 max. 40.0 Stiffness - 19.7 22.9 40.1 50.5 25 - 40 Stability kN 15.4 20.3 24.6 20.8 - 195 Deformation 10 “ ¹ mm 50.5 48.5 45.2 36.2 - Stiffness - 30.5 41.8 53.2 57.4 -

CS 270 540 Bl

Table 2

Monitored property A Mixture B AB C D A request Stability after stress kN 11.1 17.9 21.3 18.7 - Change after stress in% 72.1 88.2 86.6 90.6 - Deformation after stress 10 ¹ mm 59.4 60.2 46.3 34.0 - Change after stress in% 117.6 124.1 100.2 93.9 - Degree of stiffness after stress 18.7 29.7 46.0 55.0 Change after stress in% 51.3 71.1 86.5 95.8 min. 75%

The results apply to the mixture produced at 195 ° C.

Claims (2)

FOR OMET OF THE INVENTION 1. A process for the production of an environmentally friendly additive for honest and structural insulation bituminous materials by treating distillation residues from the production of N-cyclohexylbenzothiazolyl-2-sulfenamide by direct oxidative condensation of crude 2-mercaptobenzothiazole with sodium hypochlorite in excess cyclohexylamine from the regeneration The lower phase of the resinous bottoms product of the atmospheric distillation of cyclohexylamine from an organic phase consists of benzothiazole, cyclohexylamine, other cycloaliphatic substances, sulfur polycondensates based on benzothiazole and 2-substituted benzothiazole and emulsified water, characterized in that the lower phase the tarry bottom product was distilled at a pressure of 0.5 to 20 mbar and a temperature of 20 ⁰ to 150 ° C, the heterogeneous distillate obtained directly or after separation into an aqueous phase containing the cyclohexyl amine and benzothiazol phase returned to the process for preparing N-2-cykloheKylbenzotiazolyl -sulfenemide and the resinous distillation residue is taken as an additive to the honorary and construction-insulating bituminous materials. 2. The process defined in claim 1, characterized in that the lower layer of the primary tarry bottom product was distilled in two stages, a first stage is at a pressure of 5-20 bar and a temperature of 20 ⁰ to 100 ° C with an isolated vodná.fáza of cyclohexylamine and the second stage at a pressure of 0.6 to 5 bar and a temperature of 100 ⁰ to 150 DEG C. benzothiazole phase.